CN1152035C - Furylphosphines and organometallic complexes contg. them - Google Patents
Furylphosphines and organometallic complexes contg. them Download PDFInfo
- Publication number
- CN1152035C CN1152035C CNB99807666XA CN99807666A CN1152035C CN 1152035 C CN1152035 C CN 1152035C CN B99807666X A CNB99807666X A CN B99807666XA CN 99807666 A CN99807666 A CN 99807666A CN 1152035 C CN1152035 C CN 1152035C
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- China
- Prior art keywords
- furyl
- water
- metal
- soluble
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 125000002524 organometallic group Chemical group 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 9
- MSBPSFSYBUUPMC-UHFFFAOYSA-N furan-2-ylphosphane Chemical compound PC1=CC=CO1 MSBPSFSYBUUPMC-UHFFFAOYSA-N 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- -1 furyl carboxylate salt Chemical class 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000010948 rhodium Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 150000002240 furans Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002560 nitrile group Chemical group 0.000 claims description 6
- 150000002900 organolithium compounds Chemical class 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 150000002892 organic cations Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052744 lithium Chemical group 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- KZVLNAGYSAKYMG-UHFFFAOYSA-N pyridine-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=N1 KZVLNAGYSAKYMG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical group 0.000 claims description 2
- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- 125000004950 trifluoroalkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 7
- 238000004090 dissolution Methods 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 33
- 239000000203 mixture Substances 0.000 description 24
- 239000013256 coordination polymer Substances 0.000 description 22
- 239000003446 ligand Substances 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 238000007872 degassing Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000001721 carbon Chemical group 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 238000004679 31P NMR spectroscopy Methods 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000007037 hydroformylation reaction Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 description 2
- UFKIPBAVGKSSTN-UHFFFAOYSA-N 2-chloroethyl ethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCCCl UFKIPBAVGKSSTN-UHFFFAOYSA-N 0.000 description 2
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000007341 Heck reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000001177 diphosphate Substances 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000005669 hydrocyanation reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 1
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000005291 Rumex acetosa Nutrition 0.000 description 1
- 240000007001 Rumex acetosella Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- RVYNMHOCCBZORR-UHFFFAOYSA-N bis(furan-2-yl)-phenylphosphane Chemical compound C1=COC(P(C=2OC=CC=2)C=2C=CC=CC=2)=C1 RVYNMHOCCBZORR-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008232 de-aerated water Substances 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012207 quantitative assay Methods 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000003513 sheep sorrel Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- MYAJTCUQMQREFZ-UHFFFAOYSA-K tppts Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=C(C=CC=2)S([O-])(=O)=O)=C1 MYAJTCUQMQREFZ-UHFFFAOYSA-K 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to novel water soluble furylphosphines. It also relates to organometallic complexes comprising said furylphospines and the use of said complexes. The invention further relates to the method for preparing water soluble furylphosphines.
Description
The present invention relates to new type water-solubility furyl phosphine.
The present invention also relates to comprise the purposes of organometallic complex He this type of title complex of these furyl phosphines.
The present invention also relates to the preparation method of water-soluble furyl phosphine.
Unsubstituted three furyl phosphines are at Journal of the American Chemical Society, and 1991,113, state in V.Farina that publishes in p.9585-9595 and the article of B.Krishnan.According to this article, the system that comprises these three furyls phosphines has significant catalytic activity.
Prior art does not disclose water-soluble furyl phosphine, for example constitutes those of theme of the present invention.
New type water-solubility furyl phosphine is corresponding to general formula (I):
Wherein:
-n represents 1～3 integer,
-at least one R
2Group is represented hydrophilic radical, for example
-SO
2M ,-SO
3M ,-CO
2M or-PO
3M, M represent to be selected from the inorganic of proton or organic cation residue; Be derived from the positively charged ion of basic metal or alkaline-earth metal, wherein symbol R can represent hydrogen atom identical or differently or have the ammonium cation-N (R) of the alkyl of 1～12 carbon atom
4, be derived from other positively charged ion of its furyl-sulfinate, furyl carboxylate salt, furyl sulfonate or the water-soluble metal of furyl phosphonate,
-N (R)
3X, symbol R can represent hydrogen atom identical or differently or have the alkyl of 1～12 carbon atom in the formula, X represents the organic or inorganic negatively charged ion,
-OH，
-R
1Expression is for R
2Defined hydrophilic radical, or have alkyl or alkoxyl group, halogen atom, the nitrile group of 1～12 carbon atom or have the haloalkyl of 1～12 carbon atom,
-m represents 1 or 2,
-p represents 0～3 integer,
-when m equals 2, R
2The haloalkyl that group can be represented to have alkyl or alkoxyl group, halogen atom, the nitrile group of 1～12 carbon atom or have 1～12 carbon atom.
Term " water-soluble " or " in the water soluble " refer in every premium on currency solubilized 0.01g compound at least in this article.
The compound that water-soluble furyl phosphine of the present invention generally is general formula (I), wherein:
-n represents 1～3 integer,
-R
2The expression hydrophilic radical, for example-SO
2M ,-SO
3M ,-CO
2M or-PO
3M, M represent to be selected from the inorganic of proton or organic cation residue; Be derived from the positively charged ion of basic metal or alkaline-earth metal, wherein symbol R can represent hydrogen atom identical or differently or have the ammonium cation-N (R) of the alkyl of 1～4 carbon atom
4, be derived from other positively charged ion of its furyl-sulfinate, furyl carboxylate salt, furyl sulfonate or the water-soluble metal of furyl phosphonate,
-m represents 1 or 2,
-R
1Expression is for R
2Defined hydrophilic radical; Or-N (R)
3The X substituting group, wherein the symbol R alkyl and the X that can represent hydrogen atom identical or differently or have 1～4 carbon atom represents the organic or inorganic negatively charged ion;-OH substituting group; Alkyl or alkoxy substituent with 1～4 carbon atom; Halogen atom; Nitrile group or trifluoroalkyl,
-p represents 0～2 integer.
Another theme of the present invention is the preparation method of new type water-solubility furyl phosphine.Described preparation is that raw material carries out with precursor as the phenylbenzene furyl phosphine that do not replaced by hydrophilic radical or phenyl difuryl phosphine or three furyl phosphines generally.Described method is to introduce R on furan nucleus
2Hydrophilic radical and randomly on phenyl ring, introduce R
1Group.
For example, the furyl phosphine of formula (I) generally can be prepared as follows: make organolithium compound and R
2The electrophilic center of precursor is sulfurous gas, carbonic acid gas, chloro alkyl phosphate, pyridine-sulfonic acid or the condensation of trialkylamine sulfonic acid for example, and the organic moiety of described organolithium compound is corresponding to the compound of general formula (I), and this compound does not comprise R
2Substituting group also passes through its furan nucleus and lithium atom bonding.
Organolithium compound itself obtains the effect of precursor furyl phosphine by a kind of lithium alkali (for example butyllithium) that contains.
For the preparation method of precursor furyl phosphine, for example can be with reference to Org.Prep.Proced.Int., 27,5 (1995), p.567 reach the article of A.J.Zapata and A.C.Rondon in the further part.
Water-soluble furyl phosphine makes and might prepare the water-soluble furyl phosphine that comprises at least a formula (I) and the organometallic complex of at least a metal.
The metal that can be cooperated by water-soluble furyl phosphine generally be The Chemical RubberCompany's " chemistry and physics handbook, the 51st edition " (1970-1971) in all transition metal of periodic table of elements 1b, 2b, 3b, 4b, 5b, 6b, 7b and 8 families of publication.
Among these metals, can mention the metal that can be used as chemical reaction catalyst more especially.Therefore, as non-limitative example, can mention nickel, cobalt, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium or mercury.
The solution that comprises the compound that the organometallic complex of water-soluble furyl phosphine can be by making selected metal contacts with the aqueous solution of the water-soluble furyl phosphine of formula (I) and prepares.
The compound of described metal can be dissolved in the water or organic solvent in, this organic solvent itself and water can miscible or unmixings.
Used metal or have the oxidation state that it will have in organometallic complex in the compound, or have higher oxidation state.
Accountablely as an example be, in organometallic complex of the present invention, rhodium is oxidation state (I), and ruthenium is oxidation state (II), and platinum is oxidation state (I), and palladium is oxidation state (II), and osmium is oxidation state (O), and iridium is oxidation state (O) and nickel is oxidation state (O).
In the preparation process of organometallic complex, if metal uses with higher oxidation state, then it needs by on-the-spot reduction.
The organometallic complex that comprises the water-soluble furyl phosphine of formula (I) can be used as chemical reaction catalyst.
In moisture biphasic catalysis process, water-soluble furyl phosphine has benefited from the natural hydrophilic and the R of furan nucleus
2Synergistic effect between the natural hydrophilic of group.They have very high solubility values in water.
The catalytic chemical reaction of organometallic complex as water-soluble furyl phosphine that can involved formula (I); can mention for example hydroformylation of alkene and hydroformylation effect in the presence of rhodium complex; at ruthenium; rhodium; there are alkene down in platinum or palladium complex; aldehyde; acid; the hydrogenization of alkene acid amides and nitroaromatic; the telomerization of dienes; the isomerization of alkene; the dimerisation of ethene or vinyl cyanide; the hydrocyanation of alkene in the presence of nickel complex; furans is synthetic in the presence of ruthenium complexe; the metathesis of alkene in the presence of ruthenium complexe; the polyreaction of acrylate in the presence of nickel complex, or for example Heck or Suzuki reaction of the carbon-to-carbon coupled reaction in the presence of nickel or palladium complex.
Compound of the present invention is carrying out particularly suitable in the isomerization reaction by diene through the nitrile that hydrocyanation obtains, and more is specially adapted to 2-methyl-3-crotononitrile and is isomerizated into the process of 3 pentene nitrile.This is reflected in the production technique of adiponitrile has very big industrial value.The latter is main synthetic intermediate in the production of the monomer of polymeric amide such as hexanolactam or hexamethylene-diamine especially.
The following examples explanation the present invention.
Embodiment 1～4: the water-soluble furyl phosphine of formula (I) synthetic
Embodiment 1: 2-(diphenylphosphino) furyl-5-carboxylic acid sodium
30.3ml (47mmol) n-Butyl Lithium (measuring under 1.55M) is joined in the 500ml four neck round-bottomed flasks, described flask is used nitrogen purging in advance, and reflux exchanger, mechanical stirrer and the thermometer of all pressing dropping funnel, bubbler being housed be installed, add fast then and be in 50ml with 6.4ml (42mmol) tetramethylethylened (TMEDA) in the anhydrous diethyl ether of the nitrogen degassing.Drip and be dissolved in 50ml in advance, utilize thermopositive reaction that temperature is risen to 35 ℃ with 10.65g (42.3mmol) the phenylbenzene furyl phosphine in the anhydrous diethyl ether of the nitrogen degassing.Mixture becomes orange.
Under nitrogen gas stream, stir after 15 minutes, by
31P NMR monitors anionic formation.After the phosphine adding finished 15 minutes, this generative process was finished.
Replace reflux exchanger, the pipe of Dewar flask can be dropwise transferred to solution in installation, and described flask comprises and is immersed in about 200ml with the solidified carbon dioxide in the anhydrous diethyl ether of the nitrogen degassing.Negatively charged ion is coupled to white depositions at once.After placement is spent the night, the white solid in the ether suspension is dissolved in the saturated NaHCO of 100ml in the open
3In the solution, and the extraction mixture.Twice usefulness 30ml de aerated water extracts the ether phase again.Under cool condition with a small amount of 12N hydrochloric acid in batches the water that merges of acidifying till the neutral pH.Three times with the 50ml dichloromethane extraction this contains water.Mix organic phase, and add the 1.49g sodium hydroxide that is dissolved in several ml waters.Behind the evaporating solvent, obtain viscous tawny oil, through several times the development, in anhydrous diethyl ether the washing and through after the drying under 90 ℃ of vacuum, described oil is transformed into fine white powder.Reclaim the required product of 11.44g (36mmol), promptly productive rate is 85%.
It is characterized by:
-RMN
31P(D
2O)：δ＝25,1
-RMN
1H(D
2O)：δ＝6,20(d，1H，
3J
HH＝3,2，C
3H)；δ＝6,81(m，1H，C
4H)；δ＝7,06(m，10H，Ar)
-RMN
13C(D
2O)；δ＝117,8(s，C
3H)；δ＝124,9(m，C
4H)；δ＝131.1(d，
3J
Cp＝7,0，
C meta)；δ＝131,7(s，
C para
)；δ＝135,5(d，
2J
CP＝19,7，
C ortho )；δ＝136,8(d，
1J
CP＝4,4，
C ipso )；δ＝156,4(s，COO)；δ＝156,9(d，
1J
CP＝13,7，C
5H)；δ＝168,1(s，C
2H).
The solubleness of this furyl phosphine in 23 ℃ of water is 250g/l.
Embodiment 2: 2-(diphenylphosphino) furyl-5-phosphonic acids disodium
33.8ml (52mmol) n-Butyl Lithium (measuring under 1.55M) is joined in the 500ml four neck round-bottomed flasks, described flask is used nitrogen purging in advance, and reflux exchanger, mechanical stirrer and the thermometer of all pressing dropping funnel, bubbler being housed be installed, add fast then and be in 50ml with 6.4ml (42mmol) TMEDA in the anhydrous diethyl ether of the nitrogen degassing.Drip and be dissolved in 40ml in advance, utilize thermopositive reaction that temperature is risen to 35 ℃ with 12.32g (48.9mmol) the phenylbenzene furyl phosphine in the anhydrous diethyl ether of the nitrogen degassing.Mixture becomes orange.
Under nitrogen gas stream, stir after 15 minutes, by
31P NMR monitors anionic formation.After the phosphine adding finished 15 minutes, this generative process was finished.
Reaction mixture is cooled to-70 ℃, a pipe is installed is replaced reflux exchanger.Solution is dropwise transferred in second the four neck reactor with the identical configuration in front, and this reactor is cooled to-60 ℃ and comprise 7.3ml (49mmol) the chloro diethyl phosphoric acid that is diluted in the 20ml anhydrous diethyl ether.Before on-the-spot hydrolysis, make mixture get back to room temperature with the 100ml aqueous ammonium chloride solution.Extract with the 50ml ether for three times.Merge organic phase, and dry on sal epsom.Filter and evaporating solns, obtain 20g tawny oil.The latter is 10
-2In 100 ℃ of spherical stoves, be heated under the mm mercury column (1.3Pa), so that remove phosphoric acid ester.Reclaim 17.2g viscous tawny oil, described oil then carries out stratographic analysis with 50/50 ethyl acetate/hexane mixture as elutriant on 10cm silica gel.Behind the evaporating solvent, collect the painted oil of 14.2g, this oil is being placed and is being spent the night in the presence of 10ml (74mmol) the bromo trimethyl silane with under the magnetic agitation in the solution of 60ml methylene dichloride.Reaction is heat release, and observes the mixture decolouring.Behind the evaporating solvent, product is dissolved in 60ml acetone and the 2ml distilled water.After 2 hours 30 minutes, evaporating solvent also is dissolved in product in the small amount of methanol.Under stirring and cool condition, add the 3.04g40% aqueous sodium hydroxide solution.Form white depositions.Evaporating solvent is used the washing with acetone product, filters and drying under 100 ℃ of vacuum.Reclaim required product, productive rate is 54%.
It is characterized by:
-RMN
31P(D
2O)：δ＝28,2；d＝0,8(P＝O)
-RMN
1H(D
2O)：δ＝6,72(m，2H，C
3H，C
4H)；δ＝7,41(m，10H,Ar)
-RMN
13C(D
2O)：δ＝117,9(dd，
4J
CP＝4,67，
3J
CP＝20,0,C
3H)；δ＝124,6(dd，J
CP＝3,5，J
CP＝21,0，C
4H)；δ＝131,6(d，
3J
CP＝7,5，
C méta)；δ＝132,2(s，
C para
)；δ＝135,8(d，
2J
CP＝19,2，
C ortho )；δ＝137,8(s，
C ipso )；δ＝155,4(dd，J
CP＝7,4，J
CP＝10,4，C
5H)；δ＝165,1(d，
1J
CP＝199,0，C
2H).
The solubleness of this furyl phosphine in 20 ℃ of water is 680g/l.
Embodiment 3: 2,2 '-two (furyl-5-phosphonic acids) four sodium of Phenylphosphine two bases
42ml (65mmol) n-Butyl Lithium (measuring under 1.55M) is joined in the 500ml four neck round-bottomed flasks, described flask is used nitrogen purging in advance, and reflux exchanger, mechanical stirrer and the thermometer of all pressing dropping funnel, bubbler being housed be installed, add fast then and be in 50ml with 9.15ml (60mmol) TMEDA in the anhydrous diethyl ether of the nitrogen degassing.Drip and be diluted in 40ml in advance, utilize thermopositive reaction that temperature was risen to 35 ℃ in 30 minutes with 4.41ml (60.0mmol) furans in the anhydrous diethyl ether of the nitrogen degassing.Mixture becomes orange.
Mixture is cooled to-40 ℃, so that drip 4.2ml (30mmol) the dichlorophenyl phosphorus that is diluted in the 20ml ether.By
31After P NMR monitoring product forms, mixture is warmed up to room temperature,, adds 42ml (65mmol) n-Butyl Lithium (under 1.55M, measuring) then fast so that add 9.15ml (60mmol) TMEDA that is in the 50ml ether.Under nitrogen gas stream, stir after 15 minutes, by
31P NMR monitors anionic formation.After the phosphine adding finished 15 minutes, this generative process was finished.
Reaction mixture is cooled to-70 ℃, a pipe is installed is replaced reflux exchanger.Solution is dropwise transferred in second the four neck reactor with the identical configuration in front, and this reactor is cooled to-60 ℃ and comprise 8.95ml (60mmol) the chloro diethyl phosphoric acid that is diluted in the 20ml anhydrous diethyl ether.Before on-the-spot hydrolysis, make mixture get back to room temperature with the 100ml aqueous ammonium chloride solution.Three times with 50ml extracted with diethyl ether mixture.Merge organic phase and drying on sal epsom.Filter and evaporating solns, obtain 20g sorrel oil.The latter is 10
-2In 100 ℃ of spherical stoves, be heated under the mm mercury column (1.3Pa), so that remove phosphoric acid ester.Product then carries out stratographic analysis with ethyl acetate as elutriant on 10cm silica gel.So remove a difuryl Phenylphosphine and a phosphorylation compound.Behind the evaporating solvent, collect 3.5g clean product (productive rate: 23%).Entire reaction repeats once, is used for continuing synthetic so that obtain enough products.
The solution of 8.55g (16.6mmol) diphosphate compound in the 50ml methylene dichloride is being placed and spent the night in the presence of 9.43ml (70mmol) the bromo trimethyl silane and under the magnetic agitation.Reaction is heat release, and observes the mixture decolouring.Behind the evaporating solvent, product is dissolved in 50ml acetone and the 2ml distilled water.After 2 hours 30 minutes, evaporating solvent also is dissolved in product in the small amount of methanol.Under stirring and cool condition, add the 2.8g40% aqueous sodium hydroxide solution.Mixture is become brown by yellow.Evaporating solvent, development gained orange solids is used washing with acetone, filters and drying under 100 ℃ of vacuum.Reclaim the required product of 6.7g canescence, productive rate is 82% (with respect to the diphosphate compound).
It is characterized by:
-RMN
31P(D
2O)：δ＝49,5；d＝0,0(P＝O)
-RMN
1H(D
2O)：δ＝6,67(m，2H，C
4H)；δ＝6,80(m，2H，C
3H)；δ＝7,41(m，5H，Ar)
-RMN
13C(D
2O)：δ＝117,7(d，
3J
CP＝20,4，C
3H)；δ＝123,9(dd，
3J
CPO＝9,2，
2J
CP＝18,3，C
4H)；δ＝131,4(d，
3J
CP＝7,0，
C méta)；δ＝131,9(s，
C para
)；δ＝134,7(d，
2J
CP＝19,0，
C ortho )；δ＝136,9(s，
C ipso )；δ＝153,5(d，
1J
CP＝7,3，J
CP＝10,4，C
5H)δ＝164,5(d，
1J
CPO＝199,5，C
2H).
The solubleness of this furyl phosphine in 23 ℃ of water is 1140g/l.
Embodiment 4: 2-(diphenylphosphino) furyl-5--sulfinic acid sodium
26.3ml (40mmol) n-Butyl Lithium (measuring under 1.52M) is joined in the 500ml four neck round-bottomed flasks, described flask is used nitrogen purging in advance, and reflux exchanger, mechanical stirrer and the thermometer of all pressing dropping funnel, two bubblers (water and silicone oil) being housed be installed, drip then and be dissolved in 50ml in advance, utilize thermopositive reaction that temperature is risen to 30 ℃ with 10.65g (42.3mmol) the phenylbenzene furyl phosphine in the anhydrous diethyl ether of the nitrogen degassing.The mixture yellowing.
Under nitrogen gas stream, stir after 45 minutes, by
31P NMR monitors anionic formation.Reaction mixture is cooled to-60 ℃, nitrogen gas stream is replaced by the sulfurous gas air-flow.White depositions appears, mixture yellowing then, and become brown.Reaction is heat release.Then form the blast air of nitrogen, so that, make mixture slowly get back to room temperature with the reactor degassing.The on-the-spot then water that adds the 100ml degassing stirs mixture 1 hour.Water extraction three times.Merge and contain water,, in the presence of the 100ml methylene dichloride, use 10ml 3N hcl acidifying with the ice bath cooling.The yellow disappearance.Extract fast three times with methylene dichloride.Merge organic phase, and under mechanical stirring and cool condition, add 1.2g sodium hydroxide.The vaporising under vacuum solvent is limited to temperature and is up to 40 ℃.Obtain the required product of 6.86g (20.3mmol) (white solid); Productive rate is 51%.
It is characterized by:
-RMN
31P(D
2O)：δ＝26,7
-RMN
1H(D
2O)：δ＝6,40(m，1H，C
3H)；δ＝6,53(m，1H，C
4H)；δ＝7,06(m，10H，Ar)
-RMN
13C(D
2O)：δ＝111,6(s，C
3H)；δ＝124,8(m，C
4H)；δ＝131,1(d，
3J
CP＝7,0，
C meta)；δ＝131,7(s，
C para
)；δ＝135,5(d，
2J
CP＝19,4，
C ortho )；δ＝136,8(d，
1J
CP＝2,9，
C ipso )；δ＝156,5(d，J
CP＝16,5，C
5H)；δ＝170,1(s，C
2H).
The solubleness of this furyl phosphine in 21 ℃ of water is 205g/l.
Embodiment 5～13: the preparation of the metal complexes of the water-soluble furyl phosphine of formula (I) and these are joined
Compound is as the purposes of hydrogenation catalyst
Operate in the 50ml autoclave, the wall of autoclave is coated with Teflon
, autoclave is equipped with magnetic bar, safety valve, measuring cell, gas delivery valve and liquid and imports valve.
At first prepare various rhodium complexs (embodiment 5～8), they are used as the catalyzer of the hydrogenization (embodiment 9～13) of Z-alpha-acetamido-styracin subsequently.
The preparation method of rhodium complex is that the solution of one of water-soluble furyl phosphine of stirring 0.05mmol embodiment 1～4 preparation in 2ml water is 10 minutes under argon atmospher, this solution and 0.025mmol[Rh (COD)
2]
+PF
6 -(COD=cyclooctadiene) solution in 1ml acetone mixes.The color of mixture is by after the orange yellowing, by
31P NMR monitors.
Below table 1 provided the eigenwert of prepared Rh title complex.
Table 1
| Embodiment | The furyl phosphine | Outward appearance | δ 31P(ppm) | J Rh-P(Hz) |
| Embodiment 5 | Embodiment 1 | Transparent aureus | 14.6(d) | 144 |
| Embodiment 6 | Embodiment 4 | Transparent aureus | 15.0(d) | 148 |
| Embodiment 7 | Embodiment 2 | Transparent aureus | 12.0(d，P III) -1.7(s，P＝O) | 148 |
| Embodiment 8 | Embodiment 3 | Transparent aureus | -1.0(s，P＝O) -4.0(d，P III) | 150 |
The title complex that uses syringe to make above joins in the autoclave, adds 0.410g (2mmol) Z-alpha-acetamido-styracin solution of (volume ratio is 1/1 or 1/2) in 30ml first alcohol and water then.
Mixture keeps evenly.
(0.3～0.4MPa) hydrogen pressure stirs the mixture according to the performance and being absorbed in the variable time (referring to following table 2) of gas of furyl phosphine to form 3～4 crust.When off-test, after the degassing, reaction mixture is evaporated to dried, and pass through
1H NMR is at d
6In-the dimethyl sulfoxide (DMSO) it is analyzed.
Below table 2 compiled the eigenwert of various embodiment (title complex numbering wanted the weight ratio (%) of hydrogenant organometallic complex/matrix, H
2Pressure, the time length) and gained result (transformation efficiency of matrix).
Table 2
| Embodiment | Title complex (embodiment reference) | Title complex, wt% | The ratio of methanol | H 2Pressure | Time length | Transformation efficiency |
| Embodiment 9 | Embodiment 5 | 1.25 | 1/2 | 4.0 crust | 3.5 hour | 66％ |
| Embodiment 10 | Embodiment 5 | 1.25 | 1/1 | 3.0 crust | 4.5 hour | 95％ |
| Embodiment 11 | Embodiment 7 | 1.25 | 1/1 | 3.1 crust | 2 hours | 100％ |
| Embodiment 12 | Embodiment 6 | 0.5 | 1/1 | 3.0 crust | 18.5 hour | 8％ |
| Embodiment 13 | Embodiment 8 | 1.25 | 1/1 | 3.1 crust | 2 hours | 100％ |
Embodiment 14～16: the preparation of the metal complexes of the water-soluble furyl phosphine of formula (I) and described joining
The purposes of compound in cinnamic hydrocarbonylation
The preparation of title complex
Organometallic complex is prepared as follows: the furyl phosphine that will be dissolved in the formula (I) in the 1ml water is added drop-wise to metal precursor [Rh (CO)
2Cl]
2Or [Rh (CO)
2Acac] (abbreviation " acac " refer to " methyl ethyl diketone acid group ") produce in the solution that forms in the toluene that final all acetone of phase medium (below replaceable form (a) in table 3) or 1ml produce final heterogeneous medium (two-phase medium) (below replaceable form (b) in table 3) at 1ml.
When in heterogeneous medium, being prepared, observe yellow by transfer in the organic phase moisture mutually in, gained solution is transparent.
When being prepared in equal phase medium, part metals is with the form precipitation of the green needles of metal, and the color of medium is yellow, even is black.
Dipolymer [Rh (CO)
2Cl]
2Using as precursor need adding triethylamine (0.1ml).
At room temperature pass through
31P NMR analyzes prepared title complex.They all produce the spectrum with a broad peak (mating feature that the ligand quick exchange is arranged), as the function of used phosphine, and chemical shift δ=-10 at described peak～+ 20ppm.
Cinnamic hydroformylation reaction
The 250ml autoclave of magnetic bar, safety valve, measuring cell and two gas delivery valves is housed with argon purge.Adding toluene and the distilled water that outgases with nitrogen in advance with the transfer pipet order under argon gas stream, is catalyzer (organometallic complex) then.
Carry out the version of two kinds of tests:
-variation (a) is 8ml water/8ml toluene/2g vinylbenzene on the one hand, is 1ml acetone/1ml distilled water/0.08mmol rhodium/0.16mmol furyl phosphine on the other hand,
-variation (b) is 2.5ml water/2.5ml toluene/1g vinylbenzene on the one hand, is 1ml toluene/1ml distilled water/0.04mmol rhodium/0.08mmol furyl phosphine on the other hand.
Form the pressure of 10 crust (1MPa) carbon monoxide and 10 crust (1MPa) hydrogen.Under strong magnetic agitation in temperature (T ℃) reacting by heating mixture 18 hours.
After discharging excessive gas, the reaction mixture sedimentation is a two-phase, by the gas chromatographic analysis organic phase.The result puts in order in following table 3: the ratio of the productive rate of aldehyde (Yd) and branching aldehyde/linear aldehyde (bA/lA).
Table 3
| Embodiment | Phosphine (embodiment) | Precursor | Variation | T℃ | Yd | bA/IA |
| Embodiment 14 | Preparation embodiment 1 | [Rh(CO) 2Cl] 2 | (a) | 55℃ | 32％ | 86/14 |
| Embodiment 15 | Preparation embodiment 2 | [Rh(CO) 2acac] | (a) | 65℃ | 100％ | 83/17 |
| Embodiment 16 | Preparation embodiment 4 | [Rh(CO) 2acac] | (b) | 50℃ | 69％ | 81/19 |
Embodiment 17～26c: have not during the carbon-to-carbon coupled reaction in water-bearing media (Heck reaction)
Purposes with the metal complexes of ligand
Under argon atmospher, in the Schlenk pipe that magnetic bar is housed, add 2mmol (0.42g) iodobenzene, 3mmol (0.30g) ethyl propenoate, 3mol (0.31g) triethylamine and 3ml acetonitrile.
In medium, add 0.05mmol (11.2g) Pd (O
2CCH
3)
2, add the phospho acid ligand (0.15mmol) that is dissolved in the 0.5ml water then.
Under brute force stirs, mixture heating up is arrived preset temperature, to reach the homogenizing of medium.
Last what react, filtering solution is transferred in the funnel then so that by settlement separate.
After water and the ether washing for several times, with the formed compound of extracted with diethyl ether.
Behind the evaporating solvent, collect brown oil.
Carry out the transformation efficiency of NMR assay determination iodobenzene by proton to the brown oil collected.
The performance of used ligand, temperature of reaction and reaction times are shown in the following table 4.The transformation efficiency that iodobenzene changes into ethyl cinnamate also is shown in this table.
Used various ligands are:
-ligand A:2,2 '-phenyl phosphino--two (furyl-5--sulfinic acid) two lithiums
-ligand B:2-(diphenylphosphino) furyl-5-phosphonic acids disodium
-ligand C:2-(diphenylphosphino) furyl-5-carboxylic acid sodium
-ligand D:2,2 '-phenyl phosphino--two (furyl-5-carboxylic acid) two lithiums
-ligand E: a triphenylphosphine trisulfonic acid trisodium (ligand of prior art)
Table 4
| Embodiment | 17 | 18 | 19 | 20 | 21 | 22 | 23 | 24 | 25c | 26c |
| Ligand | A | B | C | D | E | |||||
| T℃ | 22 | 80 | 40 | 70 | 40 | 80 | 40 | 80 | 40 | 70 |
| Time length (hour) | 10 | 2.5 | 2 | 1 | 2 | 1 | 2 | 1 | 2 | 1 |
| The transformation efficiency of iodobenzene (%) | 65 | 100 | 100 | 100 | 55 | 90 | 99 | 100 | 21 | 100 |
Therefore coordination physical efficiency of the present invention obtains certain iodobenzene transformation efficiency under not too high temperature or even room temperature.
Embodiment 27～29c: the metal complexes with different ligands is at 2-methyl-3-crotononitrile
(2M3BN) purposes in the isomerization reaction of formation 3 pentene nitrile (3PN)
The aqueous solution (concentration is expressed as the mmol/kg ligand) with the water-soluble ligand L of 1.5g under argon atmospher joins in the Schlenk pipe that magnetic bar is housed.
Add two (1, the 5-cyclooctadiene) nickel (the O) (Ni (COD) of 5g 2M3BN and 40～45mg
2) be 4.5 with the mol ratio that obtains ligand/nickel in the mixture.Stirred mixture is increased to 90 ℃, and under this temperature, kept 3 hours.After the cooling, reaction mass is dissolved in the acetone and the organic compound that exists with quantitative assay by gas chromatographic analysis.Below table 5 compiled the result who obtains by several ligands, wherein two is of the present invention.
Table 5
| Embodiment | 27 | 28 | 29c |
| Ligand | 2,2 '-two (furyl-5--sulfinic acid) two lithiums of phenyl phosphino- | 2,2 '-two (furyl-5-phosphonic acids) four sodium of phenyl phosphino- | Na 3TPPTS |
| The concentration of ligand L (mmol/kg) | 500 | 800 | 500 |
| The ratio of ligand/Ni | 4.5 | 4.5 | 4.5 |
| The transformation efficiency of 2M3BN (%) | 20 | 87 | 68 |
| The productive rate of 3PN (%) | 73 | 92 | 87 |
TPPTS :-the triphenylphosphine trisulfonate
Coordination physical efficiency of the present invention has the high conversion that obtains 2M3BN under the good optionally situation for 3PN.
In table 4 and 5, embodiment 25c, 26c and 29c are the comparing embodiments of carrying out with the ligand of prior art.
Claims (9)
1, furyl phosphine is characterized in that they are water miscible and corresponding to general formula (I):
Wherein:
-n represents 1～3 integer,
-at least one R
2Group represents to be selected from the hydrophilic radical of following groups:
-SO
2M ,-SO
3M ,-CO
2M or-PO
3M, M represent to be selected from the inorganic of proton or organic cation residue; Be derived from the positively charged ion of basic metal or alkaline-earth metal, wherein symbol R can represent hydrogen atom identical or differently or have the ammonium cation-N (R) of the alkyl of 1～12 carbon atom
4, be derived from other positively charged ion of its furyl-sulfinate, furyl carboxylate salt, furyl sulfonate or the water-soluble metal of furyl phosphonate,
-R
1Expression is for R
2Defined hydrophilic radical, or have alkyl or alkoxyl group, halogen atom, the nitrile group of 1～12 carbon atom or have the haloalkyl of 1～12 carbon atom,
-m represents 1,
-p represents 0～3 integer,
-when m equals 2, R
2The haloalkyl that group can be represented to have alkyl or alkoxyl group, halogen atom, the nitrile group of 1～12 carbon atom or have 1～12 carbon atom.
2, the water-soluble furyl phosphine of claim 1 is characterized in that corresponding to general formula (I), wherein:
-n represents 1～3 integer,
-R
2Expression is selected from the hydrophilic radical of following groups:
-SO
2M ,-SO
3M ,-CO
2M or-PO
3M, M represent to be selected from the inorganic of proton or organic cation residue; Be derived from the positively charged ion of basic metal or alkaline-earth metal, wherein symbol R can represent hydrogen atom identical or differently or have the ammonium cation-N (R) of the alkyl of 1～4 carbon atom
4, be derived from other positively charged ion of its furyl-sulfinate, furyl carboxylate salt, furyl sulfonate or the water-soluble metal of furyl phosphonate,
-m represents 1,
-R
1Expression is for R
2Defined hydrophilic radical; Alkyl or alkoxy substituent with 1～4 carbon atom; Halogen atom; Nitrile group or trifluoroalkyl,
-p represents 0～2 integer.
3, the preparation method of claim 1 or 2 water-soluble furyl phosphine is characterized in that by organolithium compound and the R that is selected from sulfurous gas, carbonic acid gas, chloro alkyl phosphate, pyridine-sulfonic acid or trialkylamine sulfonic acid
2The precursor of group carries out condensation, and the organic moiety of described organolithium compound is corresponding to the compound of general formula (I), and this compound does not comprise R
2Substituting group also passes through its furan nucleus and lithium atom bonding.
4, organometallic complex is characterized in that comprising at least a water-soluble furyl phosphine and at least a metal that is selected from transition metal in the periodic table of elements 8 families of claim 1 or 2.
5, the organometallic complex of claim 4 is characterized in that comprising at least a metal that is selected from nickel, rhodium, palladium.
6, the preparation method of claim 4 or 5 organometallic complex is characterized in that making selected solution of metal compound to contact with the aqueous solution of the water-soluble furyl phosphine of formula (I).
7, the preparation method of claim 6 is characterized in that compound dissolution with described metal in water or organic solvent, and this organic solvent itself can miscible or unmixing with water.
8, claim 6 or 7 preparation method is characterized in that metal used in the compound or have the oxidation state that it will have in organometallic complexs, or have higher oxidation state.
9, the method for claim 8 is characterized in that when metal presents high oxidation state this metal is reduced by the scene.
Applications Claiming Priority (2)
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|---|---|---|---|
| FR98/06559 | 1998-05-20 | ||
| FR9806559A FR2778915B1 (en) | 1998-05-20 | 1998-05-20 | NOVEL FURYLPHOSPHINES AND ORGANOMETALLIC COMPLEXES COMPRISING THE SAME |
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| CN1152035C true CN1152035C (en) | 2004-06-02 |
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| US (1) | US6417375B1 (en) |
| EP (1) | EP1080096B1 (en) |
| JP (1) | JP2002515506A (en) |
| KR (1) | KR100404157B1 (en) |
| CN (1) | CN1152035C (en) |
| BR (1) | BR9910627A (en) |
| CA (1) | CA2333183A1 (en) |
| CZ (1) | CZ20004300A3 (en) |
| DE (1) | DE69906722T2 (en) |
| ES (1) | ES2192047T3 (en) |
| FR (1) | FR2778915B1 (en) |
| PL (1) | PL344285A1 (en) |
| RU (1) | RU2198891C2 (en) |
| SK (1) | SK17562000A3 (en) |
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| FR2932477B1 (en) * | 2008-06-17 | 2013-01-18 | Rhodia Operations | PROCESS FOR THE PRODUCTION OF NITRILIC COMPOUNDS FROM ETHYLENE-UNSATURATED COMPOUNDS |
| FR2932476B1 (en) * | 2008-06-17 | 2010-07-30 | Rhodia Operations | PROCESS FOR THE PRODUCTION OF NITRILIC COMPOUNDS FROM ETHYLENE-UNSATURATED COMPOUNDS |
| CN103012480B (en) * | 2012-12-27 | 2016-01-20 | 北京格林凯默科技有限公司 | A kind of preparation method of three (2-furyl) phosphine |
| CN114669294A (en) * | 2022-04-13 | 2022-06-28 | 宏业生物科技股份有限公司 | Composite catalyst for preparing 2, 2-di (2-tetrahydrofuryl) propane by hydrogenating 2, 2-di (2-furyl) propane |
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| FR2314910A1 (en) * | 1975-06-20 | 1977-01-14 | Rhone Poulenc Ind | Aldehyde prepn. by olefine hydroformylation in liquid phase - using catalyst system contg. sulphonated aryl phosphine and rhodium (NL 22.12.76) |
| US4880902A (en) * | 1987-08-27 | 1989-11-14 | Shell Oil Company | Copolymerization of carbon monoxide and olefin with diphosphine having heterocyclic substituents as catalyst |
| US5739396A (en) * | 1991-12-09 | 1998-04-14 | Stanford University | Asymmetric ligands useful for transition metal catalyzed bond forming reactions |
| IT1270082B (en) * | 1994-07-12 | 1997-04-28 | Univ Degli Studi Milano | HETEROAROMATIC DIPHOSPHINES AS CHIRAL BINDERS, COMPLEX BETWEEN THESE DIPHOSPHINS AND TRANSITION METALS AND USE OF THESE COMPLEXES AS CHIRAL CATALYSTS |
| IT1286497B1 (en) * | 1996-11-20 | 1998-07-15 | Italfarmaco Sud Spa | DIPHOSPHINES OF MIXED ETHEROARYL-ARYL TYPE AS CHIRAL BINDERS, RELATIVE COMPLEXES WITH TRANSITION METALS AND USE OF THESE |
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1998
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| TW568916B (en) | 2004-01-01 |
| FR2778915B1 (en) | 2000-06-30 |
| ES2192047T3 (en) | 2003-09-16 |
| PL344285A1 (en) | 2001-10-22 |
| DE69906722T2 (en) | 2004-02-05 |
| WO1999060003A1 (en) | 1999-11-25 |
| BR9910627A (en) | 2001-01-30 |
| US6417375B1 (en) | 2002-07-09 |
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| KR20010103550A (en) | 2001-11-23 |
| DE69906722D1 (en) | 2003-05-15 |
| KR100404157B1 (en) | 2003-11-01 |
| RU2198891C2 (en) | 2003-02-20 |
| FR2778915A1 (en) | 1999-11-26 |
| EP1080096B1 (en) | 2003-04-09 |
| EP1080096A1 (en) | 2001-03-07 |
| JP2002515506A (en) | 2002-05-28 |
| CA2333183A1 (en) | 1999-11-25 |
| SK17562000A3 (en) | 2001-08-06 |
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